Processes for introducing zinc micronutrients into liquid fertilizers

ABSTRACT

Zinc particulate compositions precoated with alkyl amine, alkyl phosphine, salts of such amines and phosphines or mixtures thereof, when added to conventional liquid fertilizers, avoid lumping and caking which otherwise occurs when uncoated zinc compositions are added to liquid fertilizers.

United States Patent 1191 I Field of Search 71/1, 27, 32, 64 C, 64 E,

Windgassen Mar. 12, 1974 I PROCESSES FOR INTRODUCING zmc. T 7 References Cited" MICRONUTRIENTS INTO LIQUID UNITED A ES TENTS FERTILIZERS 2,770,540 11/1956 Vierling 71/1 x Inventor; Richard J. windgassen East 3,186,828 6/1965 Baarson 6t 81. 7l/64 E Chicago, lnd. j Primary ExaminerSamih N. Zaharna [73] Ass1gnee. Standard Oil Company, Ch1cago, lll.. assistant Examiner Richard Barnes [22] Filed: Jan. 8, 1973 121 App]. No.: 321,924 371 "Xifs'fiz'AFT Related US. Application Data Zinc particulate compositions precoated with alkyl [63] Continuation of Ser. No. 129,109, March 29, 1971, amine, alkyl Phosphine, Salts of Such amines and P abandoned, which is a continuation-in-part of Ser. p m r mlxtures r n added to nv n- No. 867,905, Oct. 20, I969, abandoned. tional liquid fertilizers, avoid lumping and caking whichv otherwise occurs when uncoated zinc composi- [52] US. Cl. 71/1, 7l/27, 71/64 E, tions are added to liquid fertilizers.

v H 71/64C I 51 11 11. c1.....- C05d 9/02 2 Clam, D'awmgs PROCESSES FOR INTRODUCING ZINC MICRONUTRIENTS INTO LIQUID FERTILIZERS RELATED APPLICATIONS This application is a continuation of Ser. No. 129,109 filed Mar. 29, 1971 now abandoned which in turn was a continuation-in-part of Ser. No. 867,905 filed Oct.

20, 1969 now abandoned.

BACKGROUND OF THE INVENTION THE INVENTION I have found that particulate zinc compositions precoated with alkyl amines, alkyl phosphines, salts of said amines and phosphines or mixtures thereof can be added to a base liquid fertilizer without lumping or caking. Thus excessive agitation is avoided with attendant reduction in equipment wear and time required to make the fertilizer. Adding the coating material to the liquid fertilizer instead of precoating the zinc composition does little 'to reduce lumping. I havealso found that materials such as stearic acid, paraffin wax and motor oil have no appreciable effect'in reducing lumping and caking. Base Liquid Fertilizer Most liquid fertilizer contains at least about 30 weight percent plant nutrient such as compounds of nitrogen, phosphorus and potassium. The phosphorus .and potassium concentrations are conventionally expressed as oxides. 'The proportions of nitrogen, phosphorus .and potassium vary, as for example, 1:1:1, 1:221, 1:311, 1:3:0, 2:321, 4:311, etc.

Sources of nitrogen suitable for use in the preparation of the base fertilizer include ammonia, urea, ammonium nitrate, ammonium sulfate and mixtures thereof. Ammonia may be used in either aqueous or anhydrous form. Urea, ammonium nitrate and ammonium sulfate may be used in solid form or as an aqueous.

slurry or solution.

Phosphatic compounds suitable for use in preparing fertilizers include concentrated aqueous phosphoric acid solutions, monoammonium phosphates, diammonium phosphates, or mixtures thereof. Ammonium phosphates can be used ineither solid or aqueous form. Superphosphoric acid prepared by either the fumace process or wet process" is a preferred source.

Suitable sources of potassium are potassium salts such as potassium chloride, potassium sulfate, potassium nitrate, and the like. Potassium chloride is the preferred source.

Liquid fertilizer may also include dispersed material. For example, clay is sometimes added to the fertilizer tosuspend particles or potassium chloride or the like.

In addition to the-zinc, other micronutrients such as iron, magnesium, manganese or other metals may be included. Sometimes herbicides and pesticides are also added to the fertilizer. Particulate Zinc Composition Suitable sources of zinc include zinc sulfate (ZnSO; H O), zinc oxide, zinc carbonate, or free metallic zinc particles. Generally, these zinc compositions are powders having particles ranging in size from about to about 1,000 microns. In most instances they are present in concentrations ranging from about 0.05 to about 1.0 weight percent zinc, based on total fertilizer weight. This is normally considered an agronomically active amount, but this amount can vary somewhat depending upon the soil conditions. Coating Materials Primary, secondary and tertiary alkyl amines are all effective in reducing or eliminating lumping, but primary amines perform best and frequently cost less. Tertiary phosphines are preferred over primary and secondary phosphines because these latter materials are excessively reactive 'with oxygen. Overall, the alkyl amines are preferred over the alkyl phosphines for two reasons: First, the alkyl amines, especially the primary alkyl amines, are more effective than the alkyl phosphines in reducing lumping. Second, the alkyl amines are less costly than alkyl phosphines.

The preferred alkyl amines have the formula where R, is an alkyl group, R and R are hydrogen or alkyl groups, and the sum total of carbon atoms in the formula is at least six. Generally the alkyl amines should contain from about six to about 40 carbon atoms. Examples of suitable alkyl amines are laurylamine, oleylamine, stearylamine, n-tetradecylamine, ntetracontylamine, n-hexylamine, N,N- dimethyldodecylamine, 2-ethylhexy1amine, tri-noctylamine, di-n-nonylamine, l,8,-diaminooctane, and 1,11-diaminoundecane. Armor Industrial Chemical Company also sells a number of suitable alkyl amines such as Duomeen O (oleic 1,3 ,propylenediamine), Duomeen S (soya 1,3-propylenediamine), Armeen 18D (n-octadecylamine), and Armoflow 610.

The preferred alkyl phosphines have the'formula and phosphines are also suitablecoating materials, and

have tested oleylamine acetate and hydrochloride on zinc sulfate (ZnSO H O). I have found such salts are as effective as the oleylamine itself. The oleylamine acetate and hydrochloride were applied to the zinc sulfate in a solution of methylene chloride and ether.

If the amine has the general formula R N, where the R groups may represent different alkyl groups or alkyl and hydrogen groups, the following salts are suitable:

l. (R Nl-l) X (monovalent anion): X NO, (nitrate), Cl (chloride), Br- (bromide), H BOJ (borate), Cl-I COO- (acetate), CH (CH COO (hexanoate 2. (R NH) X (divalent anion): X SO sulfate), HPO (dibasic phosphate), etc.

3. (R Nl-l) X (trivalent anion): X sic phosphate), etc.

4. Amine salts of polymeric acids, such as polyacrylic acidor poorly characterized acids, like lignosulfonic acids.

5. Complexes of zinc salts such as (R N ),,Zn X or (R N),,Zn X etc., where y l to 4.

In general, phosphines of the type R P, where the three R groups represent different alkyl groups or alkyl and hydrogen groups, can also be used in the salt forms similar to those of groups (l)-(5) above.

Converting the amines or phosphines to salts will in general change their solubility characteristics, and new solvent systems might have to be employed for their use in coating the zinc salts.

Conventional coating techniques can be employed in precoating zinc particulate compositions. For example, coating materials may be dissolved in a suitable solvent, with the particulate compositions then being mixed with this solution. Or, the coating material and the particulate composition may be mixed together directly. If the coating material is first dissolved in the solvent, the solvent should not react with the particulate composition. Suitable solvents are, for example, heptane, xylene, petroleum distillates, dibutyl ether, and trichloroethylene.

' The amount of coating material is not critical. As little as 0.005 weight percent material, based on the weight of particulate composition, has been effective. Normally, the amount of coating material ranges from about 0.05 to about 1.50 weight percent, based on weight of particulate composition. With solid amines, the addition of excessive amounts (about 2 weight percent) leaves an obvious residue in the fertilizer. With some liquid amines, using more than about 1 weight percent tends to make the zinc particulate composition stick together. However, different coating materials behave differently, and the amounts employed will therefore vary.

Adding Metallic Zinc Particles to Base Liquid Fertilizers While investigating ways to introduce zinc micronutrients into base liquid fertilizer, l'found that free metallic particles can be added directly to the base fertilizer. When this is done some caking occurs and hydrogen gas is liberated. Since hydrogen gas and air form an explosive mixture, it is necessary to suppress the formation of hydrogen gas. This can be achieved if the base fertilizer includes an oxidizing agent in an amount sufficient to react with the expected quantity of hydrogen ordinarily produced.

Nitrate salts, nitrite salts, hydroxylamine or nitroparaffins are examples of effective oxidizing agents for suppressing the formation of hydrogen. The nitrate and nitrite salts and hydroxylamine are reduced to ammonia which dissolves in the fertilizer. The nitroparaffins,

P04 (tribahowever, are reduced to alkyl amines. Thus if the zinc particles are first precoated with nitroparaffins containing more than six carbon atoms, it is possible to suppress hydrogen formation and simultaneously prevent lumping. Nitroparaffms such as nitroethane, 2- nitrobutane, etc., up to about nitrohexane, could be used as hydrogen acceptors while nitroparaffins from about six carbon atoms up to about 40 carbon atoms could be used in smaller amounts as coating agents.

Altemately, free metal particles of zinc can be precoated with alkyl amines or alkyl phosphines so that caking is avoided. Precoating, however, does not seem to increase the rate at which the metal is dissolved in the fertilizer, but adding ammonia to the mixture does increase this dissolving rate. Preferred zinc particle size ranges between about 50 and about 100 microns. Such precoated zinc particles are dissolved in the base fertilizer which includes sufficient oxidizing agent to suppress the formation of hydrogen gas.

PREFERRED EMBODIMENTS Example I Forty grams of zinc sulfate and 0.5 grams of Armeen l8D were mixed together and warmed at C for about 1 hour in an Erlenmeyer flask. The contents of the flask were allowed to cool and then mixed with 500 grams of commercial 7 24-3 liquid fertilizer. The coated zinc sulfate tended to float on the surface of the fertilizer. Very little lumping was observed. The zinc sulfate was completely dissolved in 15 minutes as opposed to 1 hour for uncoated zinc sulfate. The uncoated material also formed lumps and required a great deal of agitation to dissolve.

Example 2 This example was substantially the same as example 1 except di-n-nonylamine was substituted for the ArmfinliiDt Example 3 This example was substantially the same as example 1 except 0.4 grams of tetradecylamine was substituted for the Armeen 18D.

Example 4 This example was substantially the same as example 1 except n-hexylamine was substituted for the Armeen 18D.

Example 5 I This example was substantially the same as example 1 except 1,8 diaminooctane was substituted for the Armeen 18D.

Example 6 This example was substantially the same as example 1 except 1,1 1 diaminoundecane was substituted for the Armeen 18D.

Example 7 This example was substantially the-same as example 1 except trioctylamine was substituted for the Armeen 18D.

Example 8 This example was substantially the same as example 1 except Duomeen O was substituted for the Armeen 18D. The Duomeen O was very effective.

Example 9 Example 10 This example was substantially the same as example 1 except zinc carbonate was substituted 'for zinc sulfate. Zinc carbonate effervesces in the liquid fertilizer, and carbon dioxide evolves. The evolution of the carbon dioxide impairs caking in the early stages of mixing; however, precoated zinc carbonate dissolves faster than uncoated zinc carbonate, and caking in the latter stages of mixing is avoided. I I

Example 1 1 With stirring, 0.3 grams of tri-n-octylphosphine and 40 grams of zinc sulfate were mixed together and heated at about 80C for about 1 minute. The precoated zinc sulfate was then dispersed in 500 grams of 7-24-3 liquid fertilizer. Precoating with the phosphine minimized lumping; however, the phosphine did not perform as well as the alltyl a lines of pre- Example 12 Five hundred grams of 3-10-8 liquid fertilizer, 30 milliliters of 15 molar ammonium hydroxide, and 10 milliliters of 28 0-0 ammonium nitrate and ureasolution (38.8 weight percent ammonium nitrate) were mixed together to give a solution of pH 8.7. With stirring, 5.0 grams of zinc dust (particles ranging in size from about 50 to about microns) was added to the solution.

The zinc particles dissolved in about 1% minutes. No

hydrogen evolved, but a small cake formed and stuck to the bottom of the reaction vessel.

Exmaple 13 This example is substantially the same as example l2 except zinc powder was first precoated with about 0.2 weight percent oleylamine. This avoided caking.

Example 14 This example is substantially the same as example 12 except 3 milliliters of nitromethane were substituted Ffifi 28-0 6 ammonium nitrate and urea solution.

I claim:

1. In the preparation of liquid fertilizer where a zinc composition in particulate form is dissolved in a base liquid fertilizer, the improvement comprising coating the particulate composition with an alkyl phosphine having the formula wherein R R and R are alkyl groups and the sum total of carbon atoms in said formula is at least six.

2. The process of claim 1 where the alkyl phosphine contains from six to about 40 carbon atoms.

I i a 14 (5/ 9) H, mm A a QERTiMQJA'm we CORRLCIlON Patent No. 3,796,559 D e March 12.1974

1nventor(s) U Richard J. Windgassen ppears in the above-identified paten't It is certified that error 2 ted as shown below;

and that said Letters Patent are hereby correc C01. 3, 'line 39% After "percent" inserfcoeting-.

C01. 5 line 35: Delete "alines of re-" p I and insert amines of previous examples.

S-igned and sealed this 1st day sfl oeeobr "1974. I

(SEAL) Attest: p M

McCOY M. GIBSON JR. c; MARSHALL'DANN I Attesting Officer Commissioner of]. Patents 

2. The process of claim 1 where the alkyl phosphine contains from six to about 40 carbon atoms. 